DE2718636A1 - AZO DYES - Google Patents

Description

The invention relates to dyes of the general formula I. ,

in the

D the remainder of a diazo component,

R is hydrogen or an optionally substituted aliphatic, cycloaliphatic, araliphatic or aromatic radical or a radical ,

R [high] 1 hydrogen, methyl, ethyl, methoxy or ethoxy,

R [high] 2 hydrogen, chlorine, bromine, methyl, ethyl, methoxy, ethoxy, C [low] 1- to C [low] 4-alkanoylamino, benzoylamino or C [low] 1- to C [low] 4-alkoxycarbonylamino ,

A [high] 1 and A [high] 2 independently of one another a C [low] 2- to C [low] 4-alkylene radical, which can optionally be interrupted by oxygen,

X is a direct bond or -O- and

Y is an optionally substituted phenyl or naphthyl radical.

The radicals D of the diazo components come predominantly from the benzene or heterocyclic series, e.g. B. the thiophene, thiazole, thiadiazole, benzthiazole, benzisothiazole, triazole, pyrazole or indazole series. Examples include:

Aniline, o-, m- or p-toluidine, o-, m- or p-methylsulfonylaniline, o-, m- or p-nitroaniline, o-, m- or p-cyananiline, o-, m- or p -Chloraniline, o-, m- or p-bromoaniline, o-, m- or p-trifluoromethylaniline, 3,4-dichloroaniline, 2,5-dichloroaniline, 3,5-dichloroaniline, 2,4,5-trichloroaniline, 2 , 4,6-trichloroaniline, 2,4,6-tribromaniline, 2,4-dicyananiline, 2,5-dicyananiline, 2-cyano-4-chloroaniline, 2-cyano-4-chloro-6-bromaniline, 2,4 -Dicyan-6-chloroaniline, 2-chloro-4-cyananiline, 2-trifluoromethyl-4-chloroaniline, 2-nitro-4-chloroaniline, 2-nitro-4-methylaniline, 2-methyl-4-nitroaniline, 2-methoxy -4-nitroaniline, 2-chloro-4-nitroaniline, 2-bromo-4-nitroaniline, 2-trifluoromethyl-4-nitroaniline, 2-trifluoromethyl-4-nitro-6-bromoaniline, 2-trifluoromethyl-4-nitro-6 -cyananiline, 2,5-dichloro-4-nitroaniline, 2,6-dichloro-4-nitroaniline, 2,6-dibromo-4-nitroaniline, 2-chloro-4-nitro-6-bromoaniline, 2,6-dichloro -4-cyananiline, 2,4-dinitroaniline, 2,4-dinitro-6-chloroaniline, 2,4-dinitro-6-bromaniline, 2,4-dinitro-6-cyano-aniline, 2,6-dicyan-4 -n itroaniline, 2-methylsulfonyl-4-chloro-aniline, 2-chloro-4-methylsulfonyl- aniline, 2-methylsulfonyl-4-nitroaniline, 2-nitro-4-ethylsulfonylaniline, 2,4-dinitro-6-methylsulfonylaniline, 2-cyano-4-methylsulfonylaniline, 2-phenylsulfonylaniline, 2,6-dichloro-4-methylsulfonyl aniline, 2,6-dibromo-4-methylsulfonylaniline, o-, m- or p-aminobenzoic acid methyl ester, ethyl ester, propyl ester, butyl ester, benzyl ester, phenyl ester, small beta-methoxyethyl ester, -small beta-ethoxyethyl ester , -small beta-hydroxyethyl ester, 4-nitroanthranilic acid methyl ester, methoxyethyl ester, 3- or 4-aminophthalic acid, 5-aminoisophthalic acid or aminoterephthalic acid dimethyl ester, diethyl ester, 3- or 4-aminobenzoic acid amide, -methylamide, -n- butylamide, methoxypropylamide, 2-, 3- or 4-aminobenzoic acid dimethylamide, diethylamide, pyrrolidide, morpholide, -N-methyl-N-small beta-hydroxyethylamide, 5-aminoisophthalic acid diamide, -dimethoxypropylamide, aminoterephthalic acid-bis-diethylamide , 3- or 4-aminophthalic acid imide, -small beta-hydroxyethylimide, -phenylimide, 3-amino-6-nitro-phtha Small acid beta-hydroxyethylimide, 2-, 3- or 4-aminobenzenesulfonic acid dimethylamide, -morpholide, -N-methylanilide, 1-amino-2-chlorobenzene-4-sulfonic acid-dimethylamide, 1-amino-2,5- or 2, 6-dichlorobenzene-4-sulfonic acid-dimethylamide, methylsulfonic acid-2'-, 3'- or 4'-aminophenyl ester, benzenesulfonic acid-2'-, 3'- or 4'-aminophenyl ester, N-acetyl-p-phenylenediamine, 2-aminobenzophenone, 1-aminoanthraquinone, 1-amino-4-chloroanthraquinone, 1-amino-2-ethoxynaphthalene, 4-amino-naphthalic acid-butylamide, 6-amino-5,7-dicyanindane, 4-aminoazobenzene, 2 ', 3 -Dimethyl-4-aminoazobenzene, 3 ', 2-dimethyl-4-aminoazobenzene, 2-methyl-5-methoxy-4-aminoazobenzene, 4-amino-2-nitroazobenzene, 2,5-dimethoxy-4-aminoazobenzene, 4' -Hydroxy-4-aminoazobenzene, 4'-chloro-4-aminoazobenzene,

2,3'-dichloroaminoazobenzene, 3,5-dibromo-4-amino-azobenzene, 4-aminoazobenzene-4'-sulfonic acid dimethylamide, 2'- or 3'-chloro-4-aminoazobenzene, benzene-azo-4-aminonaphthalene, 3 - Amino-2,1-benzisothiazole, 3-amino-5-chloro-2,1-benzisothiazole, 3-amino-5-bromo-2,1-benzisothiazole, 3-amino-5-nitro-2,1-benzisothiazole , 3-Amino-5-nitro-7-chloro-2,1-benzisothiazole, 3-amino-5-nitro-7-bromo-2,1-benzisothiazole, 3-amino-5,7-dichlorobenzisothiazole, 3 - Amino-5,7-dibromo-benzisothiazole, 4-amino-7-nitro-1,2-benzisothiazole, 4-amino-5-chloro-7-nitro-1,2-benzisothiazole, 4-amino-5-bromo -7-nitro-1,2-benzisothiazole, 4-amino-5-cyano-7-nitro-1,2-benzisothiazole, 2-aminothiazole, 2-amino-5-nitrothiazole, 2-amino-4-methyl-5 nitrothiazole, 2-amino-4-phenyl-5-nitrothiazole, 2-amino-5-phenyl-1,3,4-thiadiazole, 2-amino-5-ethylmercapto-1,3,4-thiadiazole, 3-phenyl -5-amino-1,2,4-thiadiazole, 3-small beta-carbomethoxyethylmercapto-5-amino-1,2,4-thiadiazole, 3-methylmercapto-5-amino-1,2,4-thiadiazole, 3- Aminopyrazole, 3-amino-4-cyanpyrazole, 2-phe nyl-3-amino-4-cyanpyrazole, 3-amino-5- (methyl-, ethyl-, phenyl- or benzyl) -pyrazole, 3-amino-1,2,4-triazole, 3-amino-5- ( methyl-, ethyl-, phenyl- or benzyl) -1,2,4-triazole, 3-amino-1-phenyl-pyrazole, 3-aminopyridine, 3-aminoquinoline, 2-aminobenzothiazole, 2-amino-6-methylbenzthiazole, 2-amino-6- (methoxy-, ethoxy- or butoxy) -benzthiazole, 2-amino-6-cyanobenzothiazole, 2-amino-6-thiocyanato-benzothiazole, 2-amino-6-nitrobenzthiazole, 2-amino-5, 6-dichlorobenzothiazole, 2-amino-6,7-dichlorobenzothiazole, 2-amino- (4 or 6) -methylsulfonylbenzthiazole, 2-amino-3-nitro-5-methylsulfonylthiophene, 2-amino-3,5-bis- (methyl sulfonyl) thiophene, 2-amino-3,5-dinitrothiophene, 2-amino-3-cyano-5-nitro-thiophene, 2-amino-5-nitrothiophene or 5-amino-3-methyl-isothiazole.

R radicals are, for example, C [deep] 1- to C [deep] 5-alkyl, which is also represented by chlorine, bromine, hydroxy, cyano, C [deep] 1- to C [deep] 4-alkoxy, phenoxy, C [deep ] 1- to C [deep] 8-alkanoyloxy, benzoyloxy or C [deep] 1- to C [deep] 4-alkoxycarbonyl can be substituted, C [deep] 3-C [deep] 5-alkenyl, cyclohexyl, phenyl C [deep] 1- to -C [deep] 4-alkyl, phenyl, methoxyphenyl or ethoxyphenyl.

Examples include:

Methyl, ethyl, propyl, butyl, pentyl, isopropyl, isobutyl, isopentyl, allyl, butenyl, cyclohexyl, phenyl, methoxyphenyl, ethoxyphenyl, benzyl, phenylethyl, 3-phenylpropyl, 2-phenylpropyl, 2-phenoxyethyl, chloroethyl, bromoethyl, Hydroxyethyl, 2-phenyl-2-hydroxyethyl, 2-hydroxy-3-chloropropyl, 2,3-dihydroxypropyl, 2-hydroxypropyl, 2-hydroxybutyl, 2-hydroxy-3-methoxypropyl, 3-hydroxypropyl, 2-methoxyethyl, 2- Ethoxyethyl, 2-propoxyethyl, 2-butoxyethyl, 2-benzoyloxyethyl, 2-acetoxyethyl, 2-propionyloxyethyl, 2-butyryloxyethyl, 2-isobutyryloxyethyl, n-valeryloxyethyl, i-valeryloxyethyl, i-valeryloxyethyl, propyloxyloxyethyl, caprylyloxyethyl, i-valeryloxyethyl, propyloxyloxyethyl, caprylyloxyethyl, propyloxyloxyethyl, propyloxyethyl, methylyloxyethyl, propyloxyloxyethyl, caprylyloxyethyl, propyloxyethyl, propyloxyethyl, caprylyloxyethyl, Butoxycarbonylethyl, methoxyethoxycarbonylethyl, isopropoxycarbonylethyl or isobutyryloxycarbonylethyl.

Residues R [high] 2 are in addition to those already mentioned in detail z. B .:

Formylamino, acetylamino, propionylamino, methoxycarbonylamino, ethoxycarbonylamino or butoxycarbonylamino.

The radicals A [high] 1 and A [high] 2 are z. B .:

-CH [deep] 2CH [deep] 2-, , ,

-C [deep] 2H [deep] 4OC [deep] 2H [deep] 4-.

The radicals Y can, for. B. be substituted by methyl, ethyl, methoxy, ethoxy, chlorine or bromine.

To prepare the dyes of the formula I, a diazonium compound of amines of the formula II can be used

D-NH [deep] 2 II

with a coupling component of the formula III III

realize. Diazotization and coupling have no special features compared to known processes.

Compounds of the formula III are obtained from compounds of the formula by reaction with compounds of the formula .

The reactions are expediently carried out in aprotic solvents in the presence of a base, e.g. B. pyridine made.

Dyes of the formula I a are of particular importance in the

R [high] 3 C [low] 1- to C [low] 4-alkyl, small beta-hydroxyethyl or -propyl, small beta-cyanoethyl, small beta-C [low] 1- to C [low] 4-alkoxyethyl or -propyl, phenoxyethyl or -propyl, small beta-C [deep] 2- to C [deep] 4-alkanoyloxyethyl or -propyl, small beta-C [deep] 1- to C [deep] 4-alkoxycarbonylethyl or -propyl , Cyclohexyl, allyl, benzyl, phenylethyl or phenyl,

R [high] 4 hydrogen, methyl or methoxy,

R [high] 5 hydrogen, methyl, methoxy, chlorine, acetylamino or propionylamino,

A [high] 3 -CH [low] 2CH [low] 2-, or ,

A [high] 4 -CH [low] 2CH [low] 2-, or -C [deep] 2H [deep] 4OC [deep] 2H [deep] 4- and

X is a direct bond or -O-

and D has the meaning given.

For X, -O- is preferred.

The radicals D preferably come from the benzene, thiophene, thiazole, thiadiazole, benzthiazole, benzisothiazole or azobenzene series.

Preferred diazo components are, for example, those of the formula in the

T [high] 1 hydrogen, chlorine, bromine, nitro, cyano, methylsulfonyl, ethylsulfonyl, phenylsulfonyl or C [low] 1- to C [low] 4-alkoxycarbonyl,

T [high] 2 nitro, cyano, hydrogen, chlorine, bromine, methylsulfonyl, ethylsulfonyl, phenylsulfonyl or phenylazo and

T [high] 3 are hydrogen, chlorine, bromine, nitro or cyano, as well as 2-amino-5-nitrothiophene, 2-amino-3,5-dinitrothiophene, 2-amino-3-cyano-5-nitrothiophene, 2-amino -3-nitro-5-methylsulfonylthiophene, 3-amino-5-chloro-2,1-benzisothiazole, 3-amino-5-bromo-2,1-benzisothiazole, 3-amino-5-nitro-2,1-benzisothiazole , 3-Amino-5-nitro-7-chloro-2,1-benzisothiazole, 3-amino-5-nitro-7-bromo-benzisothiazole, 4-amino-7-nitro-1,2-benzisothiazole, 4-amino -5-chloro-7-nitro-1,2-benzisothiazole, 4-amino-5-bromo-7-nitro-1,2-benzisothiazole, 4-amino-5-cyano-7-nitro-1,2-benzisothiazole , 2-amino-5-nitrothiazole, 2-amino-5-ethylmercapto-1,3,4-thiadiazole, 3-phenyl-5-amino-1,2,4-thiadiazole, 3-small beta-carbomethoxyethylmercapto-5- amino-1,2,4-thiadiazole, 3-methylmercapto-

5-amino-1,2,4-thiadiazole, 2-amino-6-methoxybenzthiazole, 2-amino-6-cyanobenzothiazole, 2-amino-6-thiocyanatobenzothiazole, 2-amino-6-nitrobenzthiazole, 2-amino-5, 6-dichlorobenzthiazole, 2-amino-6,7-dichlorobenzothiazole or 2-amino-6-methylsulfonylbenzthiazole.

The dyes of the formula I are suitable for dyeing synthetic and semi-synthetic fibers, e.g. B. cellulose acetates, polyamides and especially polyesters. The dyeings obtained have good light, wet and heat-setting fastness properties.

Some of the dyes are also suitable for the process described in German Patent 1,811,796.

In the following examples, parts and percentages are based on weight, unless otherwise stated.

example 1

8.1 parts of 2-cyano-4-nitroaniline are dissolved in 50 parts of concentrated sulfuric acid and diazotized at 0-5 ° C. with 16 parts of 45% strength nitrosylsulfuric acid. After 5 hours the excess nitrite is destroyed with urea and the solution is filtered. The diazo solution thus obtained is added dropwise at 0-5 ° C. to a solution of 16.5 parts of N-ethyl-N- (small beta-phenoxyethoxycarbonyloxyethyl) aniline in 30 parts of concentrated hydrochloric acid, 250 parts of water and 250 parts of ice. A pH of 2 is set by adding sodium acetate. After the coupling has ended, the dyestuff which has precipitated out is filtered off with suction, washed neutral and dried at 60.degree. C. under reduced pressure. 21 parts of the dye of the formula are obtained ,

which provides intense violet dyeings with good fastness properties on polyester fibers.

Example 2

7.2 parts of 2-amino-5-nitrothiazole are introduced into 20 parts of 96 percent sulfuric acid at 10 to 15 ° C., 100 parts of a mixture of glacial acetic acid and propionic acid (17: 3) are slowly added at this temperature and at 0-5 ° C is diazotized with 15 parts of 45% nitrosylsulfuric acid. After 4 hours, the resulting diazo solution is at 0-5 ° C to a solution of 17.2 parts of N-ethyl-N- (small beta-phenoxyethoxycarbonyloxyethyl) -m-toluidine in 30 parts of concentrated hydrochloric acid, 250 parts of water and 250 parts Ice added dropwise. A pH of 1.3 is set by adding sodium acetate. After the coupling has ended, the dyestuff which has precipitated out is filtered off with suction, washed neutral with water and dried at 80.degree. C. under reduced pressure. 15.5 parts of the dye of the formula are obtained ,

which provides intense blue dyeings with good fastness properties on polyesters.

Example 3

9.8 parts of 3-amino-5-nitro-2,1-benzisothiazole are introduced into 50 parts of 85% strength sulfuric acid at 10.degree.-15.degree. 16 parts of 45% strength nitrosylsulfuric acid are added dropwise to this solution at 0-5 ° C. The resulting diazo solution is stirred for 3 hours at 0-5 ° C. and then poured into a solution of 16.5 parts of N-ethyl-N- (small beta-phenoxyethoxycarbonyloxyethyl) aniline in 30 parts of concentrated hydrochloric acid, 250 parts of water and 250 parts of ice let it flow in. A pH of 1.5 is set by adding sodium acetate. After the coupling has ended, the dyestuff which has precipitated out is filtered off with suction, washed neutral with water and dried at 50.degree. C. under reduced pressure. 20.4 parts of the dye of the formula are obtained ,

which provides intense blue dyeings with good fastness properties on polyester.

Example 4

10.4 parts of 2,6-dichloro-4-nitroaniline are dissolved in 50 parts of 85% strength sulfuric acid and diazotized at 0 ° -5 ° C. with 16 parts of 45% strength nitrosylsulfuric acid. After 5 hours, the diazo solution thus obtained is poured into a solution of 16.5 parts of N-ethyl-N- (small beta-phenoxyethoxycarbonyloxyethyl) aniline in 30 parts of concentrated hydrochloric acid, 250 parts of water and 250 parts of ice at 0-5 ° C permit. A pH of 1.0 is set by adding sodium acetate. After the coupling has ended, the dyestuff which has precipitated out is filtered off with suction, washed neutral with water and dried at 70.degree. C. under reduced pressure. 21 parts of the dye of the formula are obtained ,

which provides intense brown dyeings with good fastness properties on polyester fibers.

Example 5

5.5 parts of 4-amino-5-cyano-7-nitro-benzisothiazole- (1,2) are introduced into an acid mixture of 50 parts of 85% strength sulfuric acid and 15 parts by volume of glacial acetic acid / propionic acid (17: 3) at 10 ° C . 9 parts of 45% strength nitrosylsulfuric acid are added dropwise at 0-5 ° C. and the mixture is subsequently stirred at this temperature for 4 hours. The excess nitrite is destroyed by adding urea and the resulting diazo solution is added dropwise at 0 - 5 ° C to a solution of 8.6 parts of N-ethyl-N- (small beta-phenoxyethoxycarbonyloxyethyl) -m-toluidine in 15 parts of concentrated hydrochloric acid, 125 parts of water and 125 parts of ice. A pH of 1.3 is then set by adding sodium acetate. After the coupling has ended, the dyestuff which has precipitated out is filtered off with suction, washed neutral and dried at 60.degree. C. under reduced pressure. 10.2 parts of the dye of the formula are obtained ,

which provides intensive dyeings on polyester with excellent fastness properties.

Example 6

12 parts of 2-bromo-4-nitro-6-cyananiline are dissolved in 80 parts of 85% strength sulfuric acid and diazotized with 17 parts of 45% strength nitrosylsulfuric acid at 0-5 ° C. After 5 hours, the excess nitrite is destroyed with urea and filtered. The diazo solution thus obtained is added dropwise at 0-5 ° C. to a solution of 17.2 parts of N-ethyl-N- (small beta-phenoxyethoxycarbonyloxyethyl) -m-toluidine in 30 parts of concentrated hydrochloric acid, 250 parts of water and 250 parts of ice. A pH of 1.5 is set by adding sodium acetate. After the coupling has ended, the dyestuff which has precipitated out is filtered off with suction, washed neutral and dried at 50.degree. C. under reduced pressure. 24.5 parts of the dye of the formula are obtained ,

which provides intense violet dyeings with good fastness properties on polyester fibers.

Example 7

14.9 parts of the dye from Example 6, 5 parts of pyridine, 60 parts of dimethylformamide and 4.5 parts of copper (I) cyanide are heated to 90-100 ° C. for 3 hours. The cooled solution is poured into 500 parts of water, filtered off with suction and the residue is introduced into a solution of 10 parts of iron (III) chloride in 150 parts of 10% strength hydrochloric acid. After stirring overnight, the dye is filtered off with suction, washed neutral and dried at 50 ° C. under reduced pressure. 9.5 parts of the dye of the formula are obtained ,

which provides intensive dyeings with good fastness properties on polyesters.

Analogously to the methods described, the dyes which are identified in the table below by specifying the substituents and which produce dyeings in the specified hue on polyester fibers are also obtained.

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Claims (4)

1. Azo dyes of the general formula , in the D the remainder of a diazo component, R is hydrogen or an optionally substituted aliphatic, cycloaliphatic, araliphatic or aromatic radical or a radical , R [high] 1 hydrogen, methyl, ethyl, methoxy or ethoxy, R [high] 2 hydrogen, chlorine, bromine, methyl, ethyl, methoxy, ethoxy, C [low] 1- to C [low] 4-alkanoylamino, benzoylamino or C [low] 1- to C [low] 4-alkoxycarbonylamino , A [high] 1 and A [high] 2 independently of one another a C [low] 2- to C [low] 4-alkylene radical, which can optionally be interrupted by oxygen, X is a direct bond or -O- and Y is an optionally substituted phenyl or naphthyl radical. 2. Azo dyes according to Claim 1 of the formula in the R [high] 3 C [low] 1- to C [low] 4-alkyl, small beta-hydroxyethyl or -propyl, small beta-cyanoethyl, small beta-C [low] 1- to C [low] 4-alkoxyethyl or -propyl, phenoxyethyl or -propyl, small beta-C [deep] 2- to C [deep] 4-alkanoyloxyethyl or -propyl, small beta-C [deep] 1- to C [deep] 4-alkoxycarbonylethyl or -propyl , Cyclohexyl, allyl, benzyl, phenylethyl or phenyl, R [high] 4 hydrogen, methyl or methoxy, R [high] 5 hydrogen, methyl, methoxy, chlorine, acetylamino or propionylamino, A [high] 3 -CH [low] 2CH [low] 2-, or , A [high] 4 -CH [low] 2CH [low] 2-, -CH [low] 2CHCH [low] 3 or -C [low] 2H [low] 4OC [low] 2H [low] 4- and X is a direct bond or -O- and D has the meaning given. 3. Process for the preparation of azo dyes according to claim 1, characterized in that a diazonium compound of amines of the formula II D-NH [deep] 2 II with a coupling component of the formula III III implements. 4. Dyestuff preparations for dyeing synthetic fibers, in particular polyesters, containing, in addition to the usual constituents, a dyestuff according to Claim 1.